JP2008539302A - Compositions and methods for reducing NOx emissions during fluid catalytic cracking - Google Patents

Abstract

Catalytic cracking process, preferably the composition to reduce the NO _x generated during fluidized catalyst contacting step is disclosed. The composition preferably has a Y-type zeolite, a pore size in the range of about 2 to about 7.2 angstroms, and a molar ratio of SiO ₂ to Al ₂ O ₃ of less than about 500, and zinc, iron and comprising a fluid catalytic cracking catalyst composition comprising a NO _x reducing zeolite stabilized by a metal or metal ion selected from the group consisting of mixtures. Preferably, the NO _x reducing zeolite particles are bound by an inorganic binder to form a particulate composition. Alternatively, NO _x reducing zeolite particles are incorporated into the cracking catalyst as an integral component of the catalyst. The composition according to the present invention reduces the NO _x emissions emitted from the regenerator of a fluid catalytic cracking unit operated under the conditions of the FCC process without a substantial change in catalytic cracking product conversion or yield. Presents improved effectiveness. A method of using the composition is also disclosed.

Description

Cross-reference to related applications

  This application is a continuation-in-part of US patent application serial number 10 / 909,706 filed on August 2, 2004 and US patent application serial number 10 / 909,709 filed on August 2, 2004.

The present invention relates to NO _x reduction compositions for reducing NO _x emissions and methods of their use in purification processes, particularly fluid catalytic cracking (FCC) processes. In particular, the present invention relates to NO _x offgas content released from a fluid catalytic cracking unit (FCCU) regenerator during the FCC process without substantial changes in hydrocarbon conversion or valuable catalytic cracking product yield. to a method of the NO _x reduction compositions and the use of these for reducing the.

  In recent years, concerns have increased regarding air pollution from industrial emissions of harmful nitrogen oxides, sulfur and carbon, such as in the United States. In response to these concerns, government agencies have set limits on one or more acceptable emissions of these pollutants, and the trend is clearly in the direction of increasingly strict regulations.

NO _x or nitrogen oxides in the flue gas stream exiting the fluid catalytic cracking (FCC) regenerator are a widespread problem. A fluid catalytic cracking unit (FCCU) treats a heavy hydrocarbon feed containing nitrogen compounds, some of which are contained in coke, on the catalyst as it enters the regenerator. The Cork - part of the nitrogen is finally converted into NO _x emissions in FCC regenerator or downstream CO boiler. Thus, all FCCUs that process nitrogen-containing feeds can have NO _x emissions problems due to catalyst regeneration.

In the FCC process, the catalyst particles (inventory) are continuously circulated between the catalytic cracking zone and the catalyst regeneration zone. During regeneration, coke deposited on the catalytic cracking catalyst particles in the cracking zone is removed at high temperature by oxidation with an oxygen-containing gas such as air. Removal of the coke deposits restores the activity of the catalyst particles to a point where they can be reused in the decomposition reaction. Generally, when coke is burned with oxygen deficient, the regenerator flue gas has a high CO / CO ₂ ratio and a low level of NO _x , but when burned with excess oxygen, the flue gas is at a high level. having a CO content decreased with the NO _x. Thus, CO and NO _x or mixtures of these contaminants can vary depending on factors such as unit feed rate, feed nitrogen content, regenerator design, regenerator operating mode and catalyst catalyst particle composition. In small quantities with flue gas.

By treating the NO _x gas after formation, for example (Patent Document 1), (Patent Document 2), (Patent Document 3), (Patent Document 4), (Patent Document 5), and (Patent Document 6) ( Various attempts have been made to limit the amount of NO _x gas discharged from the FCCU by post-processing the NO _x containing gas stream as described in US Pat.

Another approach is to modify the operation of the reproducing apparatus in partial burn was to process the NO _x precursors in the flue gas before the next is converted to NO _x (e.g., (Patent Document 8 ), (Patent Literature 9), (Patent Literature 10), (Patent Literature 6), (Patent Literature 11), (Patent Literature 12) and (Patent Literature 13)).

Yet another approach was to modify the operation of the regenerator to reduce NO _x emissions (eg, US Pat. (For example, (Patent Document 15), (Patent Document 16) and (Patent Document 17)). Enrichment of air by oxygen in a regenerator operating in the partial combustion mode has also been proposed (for example (Patent Document 18)).

Additives have also been used in attempts to handle NO _x emissions. (Patent Literature 19), (Patent Literature 20), (Patent Literature 21), and (Patent Literature 22) disclose the use of NO _x removal compositions to reduce NO _x emissions from FCCU regenerators. is doing. While reducing the level of (Patent Document 23) and (Patent Document 24) are also emitted during the regeneration step NO _x simultaneously, discloses a NO _x reduction composition, which promotes CO combustion during FCC catalyst regeneration process step Yes. The NO _x reduction compositions disclosed by these patents can be used as an additive circulated with the catalyst particles of the FCC catalyst or incorporated as an integral part of the FCC catalyst.

(Patent Document 25) and (Patent Document 26) disclose NO _x emission from a regenerating apparatus of FCCU by incorporating separate additive particles containing zeolite with copper attached to catalyst particles of a catalytic cracking catalyst. It is disclosed to reduce things.

Numerous additives composition used heretofore to control of the NO _x emissions are normally while increasing the production of coke, catalytic cracking products of a hydrocarbon conversion or valuable, for example, gasoline, light olefins and liquefied It has caused a significant decrease in the yield of petroleum gas (LPG). It is a highly desirable property that the NO _x additive added to the FCCU does not affect the yield of the catalytic cracking product or change the overall unit conversion. FCCU operation is typically optimized based on unit design, feed and catalyst to produce catalytic cracking product candidates and maximize refining profitability. Product candidates are based on specific purification value models. For example, during the peak summer drive season, many refiners want to maximize gasoline production and in the winter season they want to maximize the production of heating oil. In other cases, refiners may find it beneficial to produce light olefin products that can be sold in the general market or used in related petrochemical plants as feedstock.

If the NO _x reduction additive increases coke production, the FCCU has insufficient air volume to burn excess coke and may result in low feed throughput in the unit. If the additive reduces the production of low value dry gas, the production of valuable products can be further reduced. The increase in dry gas can exceed the capacity of the unit handling it and reduce the amount of feed processed. If the refiner evaluates the value of these products and the unit has the equipment needed to process excess light hydrocarbons, additives that increase the production of light olefins are desirable while the refiner's goal is If is to maximize gasoline production, this additive can reduce profitability. Light olefins are usually produced with FCCU at the expense of gasoline production. Additives that increase unit conversion may be undesirable if they affect product yield, reach unit limits, and / or reduce the amount of feed that can be processed.
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As a result, any change to the FCCU that affects product candidates or changes the ability to process the feed at the desired rate can be detrimental to refiner profitability. Therefore, a need exists for NO _x control compositions that do not significantly affect product yield and overall unit conversion.

Certain metal-stabilized zeolites exhibit increased activity and stability, has been found that reduced NO _x emissions was during catalytic cracking process. Incorporates metal-stabilized zeolite component with catalytic cracking catalyst particles containing catalytic particles of cracking catalyst, especially active Y-type zeolite, and circulated in fluid catalytic cracking unit (FCCU) during fluid catalytic cracking (FCC) process it allows the yield of catalytic cracking products produced during hydrocarbon conversion or FCC process without substantially changing or excellent NO _x control performance without affecting these results.

In accordance with the present invention, the NO _x reduction composition of the present invention typically has the ability to reduce NO _x during the FCC process and is more stable with a metal selected from the group consisting of zinc, iron, and mixtures thereof. Comprising a particulate composition containing particles of a modified zeolite component. In a preferred embodiment of the invention, the particulate zeolite component is ferrierite. In a further preferred embodiment of the present invention, the zeolite particles are bound by an inorganic binder. The binder preferably comprises silica, alumina or silica-alumina. The zeolite can be exchanged with hydrogen, ammonium, alkali metals and combinations thereof. Preferred alkali metals are sodium, potassium or combinations thereof.

In one aspect of the present invention, NO _x reduction additive compositions based on a metal stabilizing zeolite is provided. The composition, in order to reduce NO _x emissions was released from the FCCU regenerator during the FCC process, it is added to the catalyst particles circulating catalytic cracking catalyst.

In another aspect of the present invention, incorporated as an integral component of the FCC catalyst, preferably Y- type zeolite active NO _x reduction catalyst composition comprising a metal stabilized zeolite containing cracking component is provided The

In yet another aspect of the invention, while substantially maintaining the yield of hydrocarbon conversion and cracking petroleum products, to reduce NO _x emissions was released from the FCCU regenerator during the FCC process, An improved NO _x reduction composition is provided.

Another aspect of the present invention provides a method for reducing the NO _x content in the off-gas of the FCCU regenerator during the FCC process using the NO _x reduction composition according to the present invention.

Another aspect of the present invention, without substantially affecting the catalytic cracking product yield generated during hydrocarbon conversion or FCC process, to reduce the NO _x content in the off gas of the FCCU regenerator It is to provide an improved FCC method.

  These and other aspects of the invention are described in detail below.

Although some nitrogen oxides are known that are relatively stable at ambient conditions, for the purposes of the present invention, nitrogen oxides, nitrogen dioxide (the main harmful nitrogen oxides) as well as N ₂ O ₄ , N NO _x is used in this specification to represent ₂ O ₅ and mixtures thereof.

The present invention is fluidized catalytic cracking (FCC) catalyst, preferably active Y- use of certain zeolite containing NO _x reduction composition in combination with type zeolite comprising catalyst conversion of hydrocarbon feeds or an exhaustive discovery that it is very effective in reducing of the NO _x emissions released from the FCCU regenerator with substantially without change FCC process conditions yield of catalytic cracking products. The compositions of the present invention generally comprise at least one metal-stabilized zeolitic component that has the ability to reduce NO _x emissions from FCCU regenerators under FCC conditions. The zeolite zinc to provide a NO _x reducing zeolite is stabilized by a metal selected from the group consisting of iron and mixtures thereof or (metal ion). In a preferred embodiment of the invention, the zeolite is bound by an inorganic binder to form a particulate NO _x reduction composition. The particulate NO _x reduction composition may be added to the circulating catalyst particles of the catalytic cracking catalyst as a separate particle additive. In another embodiment of the invention, the zeolite stabilized with the desired metal before and after incorporation in the catalytic cracking catalyst composition is incorporated as an integral component of the catalytic cracking catalyst.

For the purposes of the present invention, the phrase “substantial change in hydrocarbon feed conversion or catalytic cracking product yield” is compared to (i) the baseline yield of the same or substantially the same product. LCO (light cycle oil) combined with LPG, residual oil and gasoline yield less than 30% relative change, preferably less than 20% relative change and most preferably less than 10% relative change Or (ii) less than 10% relative change in hydrocarbon feed conversion compared to baseline conversion, preferably less than 6.5% relative change and most preferably less than 5%. It is defined in this specification to mean either relative change. Conversion is defined as 100% x (1-resid yield-LCO yield). When the NO _x reduction composition is used as a separate additive, the baseline is operated for the same or substantially the same feed and under the same or substantially the same reaction and unit conditions. The average conversion or yield of the product in the FCCU before the additive of the present invention is added to the catalyst particles of the catalyst. When the NO _x reduction composition is integrated or incorporated into the catalytic cracking catalyst particles to provide an integrated NO _x reduction catalyst system, the significant change in hydrocarbon conversion or catalytic cracking product yield is the same. Or for the same or substantially the same feed under substantially the same reaction and unit conditions, and the NO _x reduction composition being replaced by a matrix component such as kaolin or other filler in the cracking catalyst In the same or substantially the same FCCU operated on the catalyst particles of the cracking catalyst comprising the same or substantially the same cracking catalyst composition as that containing the NO _x reduction composition Determined using baseline, defined as average conversion or yield. The percent changes identified above are: 1) G, W. Young, G.M. D. Weatherbee, and S.W. W. Davey, “Simulating Commercial FCCU Yields with the Davison Circulating Riser (DCR) pilot plant unit”, National Petroleum Refiners Association (NPR2); W. Young, “Realistic Assessment of FCC Catalyst Performance in the Laboratory”, in Fluid Catalytic Cracking: Science and Technology, J. MoI. S. Magee and M.M. M.M. Mitchell, Jr. Eds. , Studies in Surface Science and Catalysis, Volume 76, p, 257, Elsevier Science Publishers B .; V. , Amsterdam 1993, ISBN 0-444-89037-8, derived from statistical analysis of operational data obtained from the Davison circulating riser (DCR).

Zeolites useful in the present invention, when the catalytic cracking process of the decomposition conditions include zeolites, especially with the ability to reduce NO _x emissions was during FCC process in FCC conditions. In general, the NO _x reducing zeolite is less than about 500, preferably less than 250, most preferably in the range of from about 2 to about 7.2 Angstroms at a molar ratio of SiO ₂ to less than 100 _Al 2 _{O 3} fine Including zeolite with pore size. Preferably, the zeolite is ferrierite, ZSM-11, beta, MCM-49, mordenite, MCM-56, zeolite-L, zeolite rho, erionite, shabazite, clinoptilolite, MCM-22, MCM-35. , MCM-61, offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35 , SSZ-48, SSZ-44, SSZ-23, dakialdite, merlinoite, lobdarite, levin, lomontite, epistilbite, gmelinite, dysmondin, cancrinite, brewsterite, stilbite, porinite, goosecreekite, natrolite, omega Or this It is selected from the group consisting of. In a further preferred embodiment of the present invention, the NO _x reducing zeolite component is ferrierite, beta, MCM-49, mordenite, MCM-56, zeolite-L, zeolite low, erionite, shabazite, clinoptilolite, Zeolite selected from the group consisting of MCM-22, offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof. In the most preferred embodiment of the invention, the zeolite is ferrierite.

In a preferred embodiment of the present invention, the zeolite comprising the NO _x reduction composition of the present invention is at least 100 m ² / g, preferably at least 200 m ² / g, and most preferably at least 300 m ² / g. Has a surface area. In another embodiment of the present invention, the zeolite is either prior to incorporation into the binder to form a particulate NO _x reduction composition or FCC catalyst, or before stabilization with a metal or metal ion. Exchanged by a material selected from the group consisting of hydrogen, ammonium, alkali metals and combinations thereof. Preferred alkali metals are those selected from the group consisting of sodium, potassium and mixtures thereof.

The NO _x reduction composition is a stabilizing amount of, e.g., from about 1.0 to about 25 weight percent, as measured by total weight of the NO _x reduction composition as the metal oxide, preferably from about 5 to About 15
Containing at least one NO _x reducing zeolite stabilized by a metal or metal ion selected from the group consisting of weight percent, most preferably about 8 to about 12 weight percent zinc, iron and mixtures thereof. It becomes.

  Typically, the stabilization of the zeolite is performed by any method sufficient to deposit the desired stabilizing metal or metal ion in or on the zeolite component. The metal or metal ions are preferably deposited in such a way that they are present in the pores of the zeolite or are incorporated into the framework of the zeolite. This can be done in various ways, as will be appreciated by those skilled in the art.

The metal or metal ion can be incorporated into the framework of the zeolite by synthesizing the zeolite in the presence of the metal or metal ion. For example, the metal component may be added to the synthetic gel during the production of the zeolite. In the alternative, the metal or metal ion component is added along with other reaction reagents as components used in the synthesis of the zeolite, or one of the other reaction reagents such as aluminum ions used in the synthesis of the zeolite. Can be partially replaced or replaced. Stabilizing metal or metal ion, to form the NO _x reduction compositions of the present invention, for example, ion-exchange, also obtained be incorporated into the pores of the zeolite using conventional methods such as impregnation.

  A typical solid phase exchange can be performed by blending the pulverized metal salt with the zeolite and heating the two components together for a time and temperature sufficient to cause the exchange. The blend can then be washed with water to remove any non-exchanged metal ions and / or any residual salts to provide a metal exchanged zeolite.

The stabilizing metal or metal ion component is impregnated, or is usually formed on the particulate NO _x reduction composition formed by binding the NO _x reduction zeolite with an inorganic binder to form particles. It can also be exchanged by solution exchange. While the present invention is not limited to any particular method of making a particulate composition, typically the particulate NO _x reduction composition of the present invention is at least 10.0 weight percent in the final composition. an amount sufficient to provide a NO _x reducing zeolite component and at least 5.0 weight percent of the binder material, NO _x reducing zeolite, forming an aqueous slurry containing the inorganic binder and optional matrix material, thereafter Manufactured by spray drying an aqueous slurry to form particles. The spray dried particles are optionally dried at a temperature sufficient to remove volatiles for a sufficient time, such as from about 90 ° C. to about 320 ° C. for about 0.5 to about 24 hours. In a preferred embodiment of the present invention, the zeolite-containing aqueous slurry is subjected to spray drying prior to spray drying to reduce the average particle size of the material contained in the slurry to 10 μm or less, preferably 5 μm or less, and most preferably 3 μm or less. Milled. This aqueous slurry can be milled before or after incorporating the binder and / or matrix material as desired.

  The spray-dried composition has a temperature and time, preferably about 320 ° C. to about about 100 ° C., sufficient to remove volatiles and provide the binder with sufficient hardness for use in the FCCU under the conditions of the FCC process. It can be calcined at 900 ° C. for about 0.5 to about 6 hours.

  In some cases, this dried or calcined composition may be used to reduce the amount of alkali metals such as sodium or potassium in the finished product, such as ammonia or ammonium salts (eg, ammonium sulfate, ammonium nitrate, ammonium chloride). , Ammonium carbonate, ammonium phosphate, etc.) or an aqueous solution of an inorganic or organic acid (for example, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, acetic acid, formic acid, etc.).

The impregnation of the particulate NO _x reduction composition can usually be performed by dissolving a soluble metal salt in water and then impregnating the particulate composition with this solution.

It is also within the scope of the present invention that a stabilizing metal or metal ion component can be added to the feed slurry during the production of the particulate NO _x reduction composition. That, NO _x reducing zeolite, binder and any matrix components also form a feed slurry, followed be typically combined with the stabilizing metal component to form a particulate composition by spray drying as described above. Before impregnating the stabilizing metal or metal ion component or binding the NO _x reducing zeolite with an inorganic binder and forming the particulate NO _x reducing composition by ordinary solution exchange as described above, are within the scope of the present invention that may be exchanged NO _x reduction compositions Butsujo.

When the NO _x reduction composition is used as an integral component of the catalytic cracking catalyst, the stabilizing metal or metal ion can be exchanged or impregnated on the NO _x reduction zeolite before and after incorporation of the zeolite as a component of the catalyst. . Without intention to limit the incorporation of the NO _x reduction zeolite component in the cracking catalyst to any particular cracking catalyst production process, usually the zeolite component, any further zeolite, usually a USY or REUSY-type cracking catalyst The zeolite and optional matrix material are slurried in water. This slurry is milled to reduce the average particle size of the solids in the slurry to 10 μm or less, preferably 5 μm or less, and most preferably 3 μm or less. The milled slurry is combined with a suitable binder, a silica sol binder, and an optional matrix material, such as clay. This slurry is then mixed and spray dried to form a catalyst. The spray dried catalyst is optionally washed using ammonium hydroxide, ammonium salts, aqueous solutions of inorganic or organic acids and water to remove unwanted salts. The washed catalyst can be replaced with a water-soluble rare earth salt, such as rare earth chloride, nitrate, and the like.

Alternatively, the NO _x reduction zeolite component, optional further zeolite, cracking catalyst zeolite, optional matrix material, water-soluble salt of rare earth, clay and alumina sol binder are slurried in water and blended. This slurry is milled and spray dried. The spray dried catalyst is calcined at about 250 ° C to about 900 ° C. The spray-dried catalyst is then optionally washed using ammonium hydroxide, ammonium salts, inorganic or organic acid aqueous solutions and water to remove unwanted salts. In some cases, the catalyst can be replaced with a water-soluble rare earth salt after washing by any of the methods known in the art. It is within the scope of the present invention that the stabilizing metal component can be added to the catalyst feed slurry at any stage of formation of the final catalyst composition.

Usually, the stabilizing metal or metal ion, solution exchange, using the method of solid-phase exchange or any other conventional, exchange or on the final catalyst composition containing the NO _x reducing zeolite or NO _x reducing zeolite Impregnated. In a typical solution phase exchange, the zeolite is slurried in an aqueous solution containing the desired metal component. The pH and temperature of the solution are controlled to maximize the exchange of metal components on the zeolite. This material can then be filtered and washed to remove any non-exchanged metal ions and / or any remaining salts. If the metal is added by impregnation, the soluble metal salt is dissolved in water and the zeolite is impregnated with this solution. In addition, the NO _x reducing zeolite containing an alkali metal or alkaline earth metal ion, or for the conversion zeolite in hydrogen form, exchange or impregnation can take place.

The amount of the NO _x reducing zeolite used in the NO _x reduction compositions of the present invention include, but are not limited to, the type of cracking catalyst to be scheme and used to coalesce the catalytic cracking catalyst the NO _x reducing zeolite It depends on several factors including. A composition separate additive compositions of the present invention, and when comprising a particulate composition formed by binding particles of the NO _x reducing zeolite with a suitable inorganic binder, particulate The amount of NO _x reducing zeolite component present in the composition is generally at least 10, preferably at least 30, most preferably at least 40 and even more preferably at least 50 weight percent based on the total weight of the composition. Typically, the particulate additive composition has a NO _x reduction of from about 10 to about 85, preferably from about 30 to about 80, and most preferably from about 40 to about 75 weight percent, based on the total weight of the additive composition. Contains zeolite components for use.

Binder materials useful in the production of the particulate NO _x reduction composition of the present invention have the ability to bind zeolite powder to form particles having properties suitable for use in FCCU under the conditions of the FCC process. Contains any inorganic binder. Typical inorganic binder materials useful for making the compositions according to the present invention include, but are not limited to, alumina, silica, silica-alumina, aluminum phosphate, and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica-alumina and mixtures thereof. More preferably, the binder comprises alumina. Even more preferably, the binder comprises alumina peptized with acid or base. Most preferably, the binder comprises an alumina sol, such as aluminum chlorohydrol. Generally, the amount of binder material present in a particular additive composition is about 5 to about 50 weight percent, preferably about 10 to about 30 weight percent, most preferably about 15 to about 50 weight percent of the additive composition of the present invention. About 25 weight percent.

Additional materials optionally present in the particulate composition of the present invention include, but are not limited to, fillers (eg, kaolin clay) or matrix materials (eg, alumina, silica, silica-alumina, yttria, lantana, Ceria, neodymia, samaria, europia, gadolinia, titania, zirconia, praseodymia and mixtures thereof). When used, the further material is of a composition for reducing NO _x emissions was released from the FCCU regenerator with FCC conditions performance, i.e. the feed conversion or product hydrocarbon catalytic cracking catalyst Used in an amount that does not significantly adversely affect the yield. In general, the additional material comprises no more than about 70 weight percent of the composition. However, the compositions of the present invention, it is preferable that consists essentially of NO _x reducing zeolite and an inorganic binder.

  The particulate additive composition of the present invention must have a particle size sufficient for the composition to be circulated through the FCCU simultaneously with the catalytic cracking catalyst catalyst particles during the FCC process. Usually, the composition of the present invention has an average particle size of 45 μm or more. Preferably, the average particle size is from about 50 to about 200 μm, most preferably from about 55 to about 150 μm, and even more preferably from about 60 to about 120 μm. The compositions of the present invention typically have a Davison Wear Index (DI) value of less than about 50, preferably less than about 20, and most preferably less than about 15.

The particulate composition of the present invention can be circulated through the FCCU in the form of a separate particulate additive along with the main cracking catalyst. Generally, the particulate additive composition is used in an amount of at least 0.1 weight percent of the FCC catalyst catalyst particles. Preferably, the amount of additive composition used ranges from about 0.1 to about 80 weight percent, most preferably from about 1 to about 75 weight percent of the catalyst particles of the FCC catalyst. Advantageously, a specially formulated high activity catalytic cracking catalyst such as described in US patent application Ser. No. 09 / 833,603 filed Apr. 13, 2001, which is incorporated herein by reference. And, when used in combination with the disclosed high activity catalytic cracking catalyst, cracking of the cracking catalyst by dilution of catalyst particles by using catalyst particle additive levels of FCC catalyst as high as 80 weight percent It is possible to effectively reduce NO _x emissions from the FCCU regenerator without losing activity.

  As will be appreciated by those skilled in the art, the separate particulate compositions of the present invention can be added in a manner conventional to FCCUs, for example, with the catalyst input to the regenerator, or by any other convenient method. .

When integrated into FCC catalyst particles, the NO _x reducing component typically accounts for at least 0.1 weight percent of the FCC catalyst particles. Preferably, the amount of NO _x reducing component used ranges from about 0.1 to about 70 weight percent, most preferably from about 1 to about 50 weight percent of the FCC catalyst particles.

As mentioned above, to construct a cracking catalyst, the integrated FCC catalyst is typically a cracking catalyst zeolite, an inorganic binder material and optionally a matrix, filler and metal traps (eg, Ni and V traps). comprising NO _x reducing zeolite component along with other additives components such. Usually Y, USY or REUSY-type cracking catalyst zeolite provides the majority of the activity, usually from about 10 to about 75, preferably from about 15 to about 60, and most preferably, based on the total weight of the composition. It is present in the range of about 20 to about 50 weight percent. Inorganic binder materials useful in the manufacture of integrated catalyst compositions according to the present invention combine the components of the integrated catalyst to form particles having properties suitable for use in FCCU under FCC process conditions. Includes any capable inorganic material. Inorganic binder materials typically include, but are not limited to, alumina, silica, silica-alumina, aluminum phosphate, and the like and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica-alumina. Generally, the amount of binder material present in the integrated catalyst composition is less than 50 weight percent based on the total weight of the catalyst composition. Preferably, the inorganic binder material is in an amount ranging from about 5 to about 45 weight percent, more preferably from about 10 to about 30 weight percent, and most preferably from about 15 to about 25 weight percent, based on the total weight of the composition. In the integrated catalyst.

  Matrix materials optionally present in the integrated catalyst composition of the present invention include, but are not limited to, rare earth oxides such as alumina, silica-alumina, lantana, transition metal oxides such as oxides of titania, zirconia and manganese. 2A oxides such as magnesium and barium oxides, clays such as kaolin and mixtures thereof. The matrix and / or filler is typically present in the integral catalyst in an amount of less than 50 weight percent based on the total weight of the catalyst composition. Preferably, the matrix and / or filler is present in an amount ranging from about 1 to about 45 weight percent, based on the total weight of the catalyst composition.

  The particle size and wear characteristics of the integral catalyst affect the fluidization properties in the unit and determine how well the catalyst is retained in a commercial FCC unit. The monolithic catalyst composition of the present invention typically has an average particle size of about 45 to about 200 μm, more preferably about 50 μm to about 150 μm. The wearability of the integral catalyst has a DI value of less than 50, more preferably less than 20, and most preferably less than 15 as measured by the Davison Wear Index (DI).

In a preferred embodiment of the present invention, the FCC catalytic cracking catalyst contains a Y-type zeolite. NO _x reducing zeolite may be incorporated directly into separate additive or particles as added to the circulating catalyst particle catalytic cracking catalyst or Y- type zeolite-containing catalytic cracking catalyst as an integral component of the catalyst. In any case, the Y-type zeolite is present in an amount sufficient to provide adequate cracking activity in the FCCU, as readily determined by those skilled in the art. Preferably, the Y-type zeolite is present in an amount sufficient to provide a ratio of Y-type zeolite to NO _x reduction zeolite of less than 2, preferably less than 1, in the catalyst particles of the total catalyst.

Briefly stated, the FCC process involves circulating fluid catalytic cracking of feedstock consisting of particles having an average size in the range of about 50 to about 150 μm, preferably about 60 to about 120 μm, in a cyclic catalyst recycle cracking process. It involves cracking the heavy hydrocarbon feedstock into light products by contact with catalytic catalyst particles. Catalytic cracking of these relatively high molecular weight hydrocarbon feedstocks produces low molecular weight hydrocarbon products. A significant step in the cyclic FCC process is
(I) contacting the feed with a hot regenerated cracking catalyst source to produce a catalytic cracking product and an effluent comprising a spent catalyst containing coke and a strippable hydrocarbon; Catalytically cracking the feed in a catalytic cracking zone operated under cracking conditions, usually a riser cracking zone
(Ii) discharging the effluent and separating it into a vapor phase rich in catalytic cracking product, usually in one or more cyclones, and a solid rich phase comprising spent catalyst;
(Iii) removing the vapor phase as product and fractionating in the FCC main column and associated side columns to form gas and liquid cracking products including gasoline;
(Iv) usually stripping the spent catalyst with steam to remove clogged hydrocarbons from the catalyst, and then oxidatively regenerating the stripped catalyst in the catalyst regeneration zone, A regenerated catalyst is produced and recycled to the cracking zone to break down additional amounts of feed.

  Conventional FCC catalysts are described in, for example, a zeolite component including a seminar review by Venuto and Habb, “Fluid Catalytic Cracking with Zeolites Catalysts”, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1. As well as Sadeghbeigi, “Fluid Catalytic Cracking Handbook”, Gulf Publ. Co. Including many other sources of information such as Houston, 1995, ISBN 0-88415-290-1. Preferably, the FCC catalyst is a catalyst comprising a Y-type zeolite active cracking component. In a particularly preferred embodiment of the invention, the FCC catalyst is packed with a binder, usually silica, alumina or silica-alumina, a Y-type zeolite active ingredient, one or more matrix alumina and / or silica-alumina and kaolin clay. It consists of an agent. Y-type zeolites can exist in one or more forms and can be super-stabilized and / or treated with stabilizing cations such as any of the rare earths.

  A typical FCC process is carried out at a catalyst regeneration temperature of 600 ° C to 800 ° C and a reaction temperature of 480 ° C to 600 ° C. As is well known in the art, the catalyst regeneration zone can consist of a single or multiple reactor vessels. The compositions of the present invention can be used in FCC processing of any typical hydrocarbon feedstock. Suitable feedstocks are petroleum distillates or crude oils having a boiling range of about 150 ° C. to about 900 ° C., preferably about 200 ° C. to about 800 ° C., which are catalytically cracked to provide gasoline or other petroleum products. Of residue. Synthetic feeds having a boiling point of about 200 ° C. to about 800 ° C., such as oil from coal, tar sand or shale oil, can also be included.

  Oxygen or air is added to the regeneration zone to remove coke from the catalyst. This is done with a suitable sprinkler at the bottom of the regeneration zone, or if desired, additional oxygen is added to the lean or dense phase of the regeneration zone.

The additive composition according to the present invention substantially maintains the hydrocarbon feed conversion or yield of catalytic cracking products obtained from cracking catalysts, such as gasoline and light olefins, while maintaining the FCCU regenerator during catalyst regeneration. Reduces NO _x emissions in the exhaust gas dramatically, ie at least 10%, preferably at least 20%. In some cases, using the compositions and methods of the present invention, without significantly affecting the yield or feed conversion in catalytic cracking products, it is easily achievable NO _x reduction of 70% or more. However, as will be understood by those skilled in the FCC art, the degree of the NO _x reduction, for example, composition and amount of additives used; but are not limited to, oxygen levels and air distribution in the regenerator, regeneration Catalytic cracking unit including catalyst bed depth in the unit, stripping unit operation and regenerator temperature, cracked hydrocarbon feedstock properties and presence of other catalyst additives that may affect the regenerator chemistry and operation Depends on factors such as the design and method of driving. Thus, since each FCCU differs in some or all of these points, the effectiveness of the method of the present invention is expected to vary from unit to unit. NO _x reduction compositions of the present invention also prevents a significant increase in the production of coke during the FCC process.

In order for the NO _x reduction composition of the present invention to achieve NO _x reduction more efficiently than using either the composition alone or alone, with one or more additional NO _x reduction components It is within the scope of the present invention that it can be used in combination. Preferably, this further NO _x reducing component is a non-zeolitic material, ie, a material that does not contain or is substantially free of zeolite (ie, less than 5 weight percent, preferably less than 1 weight percent).

  For example, in combination with other additives conventionally used in FCC processes such as SOx reducing additives, gasoline-sulfur reducing additives, CO combustion promoters, additives for the production of light olefins It is also contemplated within the scope of the present invention that additive compositions can be used.

It is not intended that the scope of the invention be limited in any way by the examples described below. Examples include the evaluation of the method of manufacture and the present invention useful additives in the methods of the present invention for reducing the NO _x in the catalytic cracking environment. The examples are presented as specific illustrations of the claimed invention. However, it should be understood that the invention is not limited to the specific details set forth in the examples.

  All parts and percentages in the examples and the rest of the specification, which refer to solid compositions or concentrations, are by weight unless otherwise specified. The concentration of the gas mixture is by volume unless otherwise specified.

  Furthermore, any number of ranges stated in this specification or claims, such as those representing a particular set of properties, units of measure, conditions, physical states or percentages, are thus stated. Any number falling within such a range, including any sub-set of numbers within that range, is intended to be incorporated literally by reference or otherwise explicitly.

The performance evaluation of the additives A to H for reducing NO emissions from the FCC unit was performed by using DCR. In each experiment, the amount of air added is defined as a sufficient condition to convert all the coke species on the FCC catalyst spent before exiting the reproducing apparatus to CO ₂ to the reproducing apparatus, The DCR was operated under “full burn” regeneration conditions. This test was performed on a regenerator operating at 705 ° C. with 1% excess O ₂ in the regenerator.

Example 1
A composition comprising 75% ferrierite and 25% alumina sol was prepared as follows: aluminum chlorohydrol solution (23% solids), 75% ferrierite (SiO ₂ / Al ₂ O ₃ = 20 Na ₂ O + K ₂ O = 6-10 wt%) and about 42-44%
An aqueous slurry containing 25% Al ₂ O ₃ was made from enough additional water to make a slurry containing This slurry was milled to an average particle size of less than 3.0 μm and then spray dried. The spray-dried product was baked at 400-450 ° C. for 20-40 minutes. The calcined catalyst was washed with ammonium sulfate solution followed by water to reduce the K ₂ O level to less than 1.0 wt%. This catalyst is named Additive A and the properties are shown in Table 1 below.

Example 2
A composition comprising 73% ferrierite, 2.5% ZnO and 24.5% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol solution (23% solids), 4500 g (dry basis) Of ferrierite (SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O + K ₂ O <0.5 wt%), 250 g ZnCl ₂ and enough additional to produce a slurry containing about 44% solids An aqueous slurry containing water was prepared. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst is named Additive B and the properties are shown in Table 1 below.

Example 3
A composition comprising 72.1% ferrierite, 3.9% ZnO and 24% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol solution (23% solids), 4500 g (dry basis) Of ferrierite (SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O + K ₂ O <0.5 wt%), 400 g ZnCl ₂ and enough additional to produce a slurry containing about 44% solids An aqueous slurry containing water was prepared. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst is named Additive C and the properties are shown in Table 1 below.

Example 4
A composition comprising 70.7% ferrierite, 5.8% ZnO and 23.5% alumina sol was prepared as follows. 6520 g aluminum chlorohydrol solution (23% solids), 4500 g (dry basis) ferrierite (SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O + K ₂ O <0.5 wt%), 600 g ZnCl ₂ and An aqueous slurry was made containing sufficient additional water to produce a slurry containing about 44% solids. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst is named Additive D and the properties are shown in Table 1 below.

Example 5
A composition comprising 69.5% ferrierite, 7.4% ZnO and 23.1% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol solution (23% solids), 4500 g (dry) Standard) ferrierite (SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O + K ₂ O <0.5 wt%), sufficient to produce a slurry containing 800 g ZnCl ₂ and about 44% solids. An aqueous slurry containing additional water was prepared. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst is named Additive E and the properties are shown in Table 1 below.

Example 6
A composition comprising 67% ferrierite, 10.7% ZnO and 22.3% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol solution (2
3% solids), 4500 g (dry basis) ferrierite (SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O + K ₂ O <0.5 wt%), containing 1200 g ZnCl ₂ and about 44% solids An aqueous slurry containing enough additional water to produce a slurry was made. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst is named Additive F and the properties are shown in Table 1 below.

Example 7
Additive G was prepared as follows: A sample of Additive D, 732.2 g dry basis, prepared as shown in Example 4, was prepared from 172.9 g Zn acetate · 2H ₂ O, 281 ml H ₂ O And impregnated with a solution prepared with 209.4 ml of 30% NH ₄ OH solution. This was oven dried at 287 ° C. for 4 hours, re-impregnated with a solution of the same composition, and dried at 287 ° C. for 4 hours. The sample was then fired at 593 ° C. for 2 hours. Additive G had the properties shown in Table 1.

Example 8
A composition comprising 62.5% ferrierite, 10.7% ZnO, 4.5% Catapal C alumina and 22.3% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol. Solution (23% solids), 4200 g (dry basis) of ferrierite (SiO ₂ / Al ₂ O ₃ = 20, Na ₂ O + K ₂ O <0.5 wt%), 300 g (dry basis) of Catapal C alumina, 1200 g An aqueous slurry containing enough additional water to produce a slurry containing about 44% solids of ZnCl ₂ was prepared. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst is named Additive H and the properties are shown in Table 2 below.

Example 9
A composition comprising 65% ferrierite, 15% clay and 20% alumina sol was prepared as follows: 4344 g aluminum chlorohydrol solution (23% solids), 3250 g (dry basis) ferrierite. An aqueous slurry was made containing sufficient water to produce a slurry containing 650 g (dry basis) of clay and about 40% solids. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst, whose properties are shown in Table 2 below, was named Additive I.

Example 10
Ferrierite was exchanged with zinc ions using solid phase exchange as follows: Zinc chloride (228 g) was ground to a fine powder and then blended with 2500 g of ferrierite powder. The blend was fired at 325 ° C. for 2 hours. This calcined blend was slurried in 9000 g of water maintained at 80 ° C., mixed for 0.16 hours, and then filtered. The filter cake was then washed 3 times with water maintained at 80 ° C., dried and then calcined at 593 ° C. for 1.5 hours. The final zinc solid phase exchanged product contained 2.80% ZnO.

  A composition comprising 65% Zn / ferrierite, 15% clay and 20% alumina sol was prepared as follows: 2608 g of aluminum chlorohydrol solution (23% solids), 1950 g (dry basis) of An aqueous slurry was made containing ferrilite which was solid phase exchanged with zinc and sufficient additional water to produce a slurry containing about 40% solids. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst was named additive J and the properties are shown in Table 2 below.

Example 11
The following method was used to prepare a ferrierite catalyst bound by silica sol: an aqueous slurry containing 29% ferrierite (SiO ₂ / Al ₂ O ₃ = 20) was milled in a dry smill. This milled ferrierite slurry (4160 g) was combined with 1200 g Natka clay (dry basis) and 6000 g silica sol binder (10% solids). This silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray dried in a Bowen spray dryer. The resulting spray-dried product was washed with ammonium sulfate solution followed by water to give a catalyst with a Na ₂ O level of less than 0.1% by weight. This catalyst was named Additive J and had the properties shown in Table 2 below.

Example 12
Additive K prepared in Example 11 was exchanged with zinc ions by the following method: 150 g of spray dried catalyst was converted to 12.4 g of Zn (NO ₃ ) ₂ . Zn exchange was performed by adding 6H ₂ O to a zinc nitrate solution containing 1500 g of water. The mixture was stirred at 70 ° C. for 0.5 hour. The slurry was then filtered and the catalyst was washed three times with water maintained at 70 ° C. to remove excess zinc nitrate. This catalyst was named additive L and had the properties shown in Table 2 below.

Example 13
Additives A-H were evaluated in the DCR to determine the effectiveness of the additive to reduce NO emissions released from the FCC unit. In each of these experiments, under “full-burn” regeneration conditions, defined as conditions where the amount of air added to the regenerator is sufficient to convert all coke species on the spent FCC catalyst to CO _2. The DCR was operated. This test was performed on a regenerator operating at 705 ° C. with 1% excess O ₂ in the regenerator.

A commercial FCC feed having the properties shown in Table 3 below was used for the test. Approximately 1596 g of an equilibrium catalytic cracking catalyst having the properties shown in Table 4 and a Pt-based combustion accelerator deactivated for 20 hours at 788 ° C. without addition of Ni or V using a cyclic propylene steaming method (CPS) ( A blend of 4 g of a commercial sample of CP®-3 (obtained from Grace Davison) was loaded into the DCR. The CPS method is described in L.C. T.A. Book, T .; F. Petti, and J.M. A. Rudesill, “Continant-Metal Deactivation and Metal-Dehyrogenation Effects Duric Cyclic Propylene Steaming of
Fluid Catalytic Cracking Catalysts ", Deactivation and Testing of Hydrocarbon Processing Catalysts, ACS Symposium Series 634, p. 171 (1996), ISBN 0-8412-3411-6.

After the unit was stabilized, baseline NO emissions data was collected using an on-line Multigas 2030 FTIR gas analyzer. Subsequently, a second blend containing this additive is injected into the DCR. For Additives A, E, F, G and H, this blend was hydrothermally non-added in a fluidized bed reactor with 20% steam in N _{2 with} no Ni or V added at 760 ° C. for 24 hours. It contained approximately 86 g of this additive activated and CP®-3 deactivated with 0.215 g CPS. For Additives B, C and D, this blend was hydrothermally deactivated at 760 ° C. for 24 hours with 20% steam in N _{2 with} no Ni or V added in a fluid bed reactor. It contained approximately 90 g of additive, 109.5 g of equilibrium catalytic cracking catalyst and 0.25 g of CPS deactivated with CPS. As seen in Table 5, Additives B~H exhibit good NO _x reduction performance than Additive A at similar amounts in DCR. This is added to ferrierite deactivation after Zn is assumed credible that improve NO _x reduction performance. NO _x reduction performance increases with increasing Zn levels until a maximum in the range of 10% ZnO.

Additives A, the yield for the run by E and F are shown in Table 6 below illustrate the point that none affect FCC yields of these of the NO _x reduction additive.

Example 14
To reduce NO _x emissions of the FCC unit, the additives I and J were evaluated in DCR. This test was performed with DCR operating under the same conditions, equilibrium catalyst and feed as Example 13. Initially, the DCR was charged with a blend of approximately 1895.25 g of equilibrium catalytic cracking catalyst and 4.75 g of CPS deactivated CP®-3. After the unit was stabilized, baseline NO emissions data was collected using an on-line Multigas 2030 FTIR gas analyzer. Subsequently, approximately 105 g of Additive I or J, 94.5 g of equilibrium catalyst and 0.5 g of CPS deactivated CPI®-3 blend were injected into the DCR and the run was run. Continued on additive for approximately 10 hours. As shown in Table 7, additives J is was the only are somewhat more effective than the additive I in reducing 1 hour after NO _x emissions, shows the advantages of the large NO _x reduction performance after 7 hours. From this data, it can be concluded that the addition of pre-exchanged Zn to ferrierite stabilizes NO _x reduction activity and results in improved NO _x reduction performance compared to unstabilized additives. it can.

Example 15
Using the same operating conditions as in Example 13 and 14 were evaluated additive K and L for NO _x reduction performance in a DCR. A commercial FCC feed was used for testing and its properties are shown in Table 8 below. Approximately 1800 g of a commercial catalytic cracking catalyst, SuperNova (registered trademark), obtained from Grace Davison, hydrothermally deactivated at 816 ° C. for 4 hours with 100% steam without addition of Ni or V in a fluid bed reactor. ) The DMR + blend was loaded into the DCR. After stabilizing the unit, using online Lear-Siegler SO ₂ / NO Analyzer (SM8100A), were collected baseline NO emissions data. Subsequently, a blend of 100 g catalyst consisting of 95.25 g hydrothermally deactivated SuperNova® DMR + catalyst and 4.75 g CPS-CP®-3 was added to the DCR. If NO emissions were collected continuously during this time frame and the unit was re-stabilized, 0.1 g with 105 g of additive K or L and 105 g of deactivated SuperNova® DMR + catalyst. A blend containing 525 g of deactivated CP-3® was added to the DCR. As can be seen in Table 9, Additive L was better than Additive K in terms of reducing NO emissions from the DCR. This indicates that post exchange of Zn to ferrierite contained in the particles by the silica sol binder improves the NO reduction performance of the ferrierite.

Example 16
A composition comprising 75% clay and 25% alumina sol was prepared as follows: 2174 g aluminum chlorohydrol solution (23% solids), 1500 g (dry basis) clay and about 40% solids. An aqueous slurry was made containing sufficient additional water to make the containing slurry. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst was named Additive M and had the properties shown in Table 10 below.

Example 17
A composition comprising 71% clay, 6% ZnO and 23% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol solution (23% solids), 45
An aqueous slurry was made containing enough water to make a slurry containing 00 g (dry basis) clay, 620 g ZnCl ₂ and about 45% solids. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst was named Additive N and had the properties shown in Table 10 below.

Example 18
ZnO supported on alumina was prepared as follows: 1000 g (dry basis) of HiQ alumina (obtained from Alcoa) was impregnated to 165 g ZnCl ₂ dissolved in water to incipient wetness. . The material was then fired at 593 ° C. for 2 hours. This catalyst was named Additive 0 and had the properties shown in Table 10 below.

Example 19
In order to simulate the absorption of SiO ₂ and sodium ions of the ZnO / alumina catalyst upon deactivation in the FCC unit, the catalyst was first impregnated with the SiO ₂ compound and then with the sodium salt. 500 g (dry basis) of Additive O was impregnated with 85 g of tetraethyl orthosilicate dissolved in ethanol to an incipient wetness. The catalyst was dried overnight at room temperature and then impregnated with an aqueous solution containing 4.3 g of sodium carbonate. The material was then fired at 593 ° C. for 2 hours. Subsequently, this sample was subjected to hydrothermal deactivation in a fluidized bed reactor with 100% steam at 816 ° C. for 4 hours. This catalyst was named Additive P and had the properties shown in Table 10 below.

Example 20
Using the same conditions, feed and catalyst as shown in Examples 13 and 14, the performance of HiQAl ₂ O ₃ and additives MP to reduce NO emissions was evaluated in DCR. Initially, this DCR was charged with a blend of 1596 g of equilibrium catalytic cracking catalyst and CP®-3 deactivated with 4 g of CPS. Once the unit was stabilized, a blend of 85.12 additive and 0.215 g of deactivated CP®-3 was charged to the DCR, and the run was run on each additive for approximately 2 hours. Continued. The results are shown in Table 11 below.

As shown in Table 11, the addition of the different ZnO carrier does not improve NO _x reduction activity in DCR, that under realistic FCC conditions specific of the NO _x reduction activity of Zn means that extremely low I can guess that. This data shows that the increase in NO _x reduction activity seen by addition of Zn to ferrierite in Examples 13 and 14 is mainly due to the stabilizing effect of Zn on ferrierite.

Example 21
A composition comprising 75% ferrierite and 25% alumina sol was prepared as described in Example 1. The spray dried product was calcined at 593 ° C. for 1.5 hours. Subsequently, the material of about 125g were dissolved in deionized water 100 ml, was impregnated with _YCl 3 · 6H ₂ 0 in 17.7 g, overnight oven drying at 287 ° C., and calcined for 2 hours and then at 538 ° C. . The resulting sample was named Additive Q and had the properties shown in Table 12 below.

Example 22
A composition comprising 75% ferrierite and 25% alumina sol was prepared as described in Example 1. The spray dried product was calcined at 593 ° C. for 1.5 hours. Subsequently, about 125 g of this material was impregnated with 33.2 g MgCl ₂ .6H ₂ O dissolved in 87 ml deionized water, oven dried at 287 ° C. overnight and then calcined at 538 ° C. for 2 hours. The resulting sample was named Additive R and had the properties shown in Table 12 below.

Example 23
A composition comprising 73% ferrierite, 3% Fe ₂ O ₃ and 24% alumina sol was prepared as follows: 6520 g aluminum chlorohydrol solution (23% solids), 4500 g (dry basis) Of clay (SiO ₂ / Al ₂ O ₃ = 20, K ₂ O <0.5 wt%), sufficient to produce a slurry containing 445 g FeCl ₂ .4H ₂ O and about 44% solids An aqueous slurry containing water was prepared. This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst was named Additive S and had the properties shown in Table 12 below.

Example 24
A composition comprising 67% ferrierite, 11% Fe ₂ O ₃ and 22% alumina sol was prepared as follows: 6520 g of an aluminum chlorohydrol solution (23
% Solids), slurry containing 4500 g (dry basis) of clay (SiO ₂ / Al ₂ O ₃ = 20, K ₂ O <0.5 wt%), 1782 g of FeCl ₂ .4H ₂ O and about 44% solids. An aqueous slurry was prepared containing sufficient additional water to produce This slurry was milled in a dry mill to an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray dried product was calcined at 593 ° C. for 1.5 hours. This catalyst was named Additive T and had the properties shown in Table 12 below.

Example 25
Using the same conditions, feed and catalyst as shown in Example 13, the performance of the additives Q-T to reduce NO emissions in the DCR was evaluated. First, a blend of 1596 g of equilibrium catalytic cracking catalyst and 4 g of CPS deactivated CP®-3 was charged to the DCR. Once the unit was stabilized, 85.12 g of additive was hydrothermally deactivated at 760 ° C. for 24 hours with 20% steam in N ₂ without addition of Ni or V in a fluid bed reactor. A blend of Q or R or S and 0.215 g of deactivated CP®-3 was charged to the DCR and the run was continued on each additive for approximately 2 hours. To evaluate additive T, the second blend was made up of 85 g hydrothermally deactivated additive, 14.75 g equilibrium catalyst and 0.25 g deactivated CP®. -3. As can be inferred from Table 13, at a fixed mole number of stabilizing metal, Zn and Fe exhibit similar NO _x reduction performance on ferrierite, and Mg or Y in the stabilized ferrierite Improved NO _x reduction performance was demonstrated.

Claims (41)

a) an effective NO _x reduction amount comprising a NO _x reduction zeolite having a pore size in the range of about 2 to about 7.2 angstroms and a molar ratio of SiO ₂ to Al ₂ O ₃ of less than about 500; in the presence of the NO _x reduction composition, the hydrocarbon feedstock is contacted with the catalyst particles and FCCU in the circulation of FCC catalytic cracking catalyst, the stabilizing said zeolite zinc, is selected from the group consisting of iron and mixtures thereof stabilized by the amount of metal or metal ion, and have the ability to reduce NO _x emissions was during FCC process and said FCCU having a regeneration zone, and is operated under the conditions of the FCC process; and b) compared to the amount of the NO _x emissions released in the absence of the NO _x reduction composition, child reduce the amount of the NO _x emissions released from the regeneration zone of the FCCU Comprising a, improved reduction method of the NO _x emissions of hydrocarbons feedstock from regeneration zone of a fluid catalytic cracking unit (FCCU) at which the fluid catalytic cracking to low molecular weight component (FCC).   The process of claim 1 wherein the FCC cracking catalyst comprises a Y-type zeolite.   Stage without substantial change in hydrocarbon feedstock conversion or catalytic cracking hydrocarbon yield compared to hydrocarbon feedstock conversion or catalytic cracking hydrocarbon yield obtained from catalytic cracking catalyst alone ( The method of claim 1, wherein b) is performed. NO _x reducing zeolite is ferrierite, ZSM-11, beta, MCM-49, mordenite, MCM-56, zeolite -L, zeolite low, erionite, Shabazaito, clinoptilolite, MCM-22, MCM-35 , MCM-61, offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, dachaldite, merlinoite, lobdarite, levin, lomontite, epistilbite, gmelinite, dysmondin, cancrinite, brewsterite, stilbite, porinite, goosecreekite, natrolite, omega or These blends The method of claim 1, wherein the method is selected from the group consisting of compounds. NO _x reducing zeolite is ferrierite, beta, MCM-49, mordenite, MCM-56, zeolite -L, zeolite low, erionite, Shabazaito, clinoptilolite, MCM-22, offretite, A, ZSM-12, 5. The method of claim 4, wherein the method is ZSM-23, omega and mixtures thereof. NO _x reducing zeolite is ferrierite, A method according to claim 5. The method of claim 1, wherein the NO _x reduction composition is present as a separate particulate additive. The method according to claim 7, wherein the particulate NO _x reduction composition has an average particle size of 45 μm or more. NO _x reduction compositions are alumina, silica, silica - alumina, it is selected from phosphoric acid alumina and mixtures thereof, further comprising from about 5 to 50 weight percent of an inorganic binder, in claim 8 The method described. The amount of the NO _x reducing zeolite present in the particulate NO _x reduction composition is at least 30 weight percent of the composition, The method of claim 9. The amount of the NO _x reducing zeolite present in the particulate NO _x reduction composition is at least 40 weight percent of the composition, The method of claim 10. The amount of the NO _x reducing zeolite present in the particulate NO _x reduction composition is at least 50 weight percent of the composition, The method of claim 11. The amount of the NO _x reducing zeolite present in the particulate NO _x reduction composition ranges from about 10 to about 85 weight percent of the composition, The method of claim 9. The amount of the NO _x reducing zeolite present in the particulate NO _x reduction composition ranges from about 30 to about 80 weight percent of the composition, The method of claim 13. The amount of the NO _x reducing zeolite present in the particulate NO _x reduction composition ranges from about 40 to about 75 weight percent of the composition, The method of claim 14.   The method according to claim 9, wherein the inorganic binder is alumina.   The process according to claim 16, wherein the alumina is peptized with acid or base.   The process according to claim 17, wherein the alumina is aluminum chlorohydrol. The amount of inorganic binder present in the NO _x in the reduction composition ranges from about 10 to about 30 weight percent of the composition, The method of claim 9. The method of claim 19, wherein the amount of inorganic binder present in the NO _x reduction composition ranges from about 15 to about 25 weight percent of the composition. The method of claim 1, wherein the NO _x reducing zeolite component has a SiO ₂ to Al ₂ O ₃ molar ratio of less than 250.   Claim 9 further comprising a matrix material selected from the group consisting of alumina, silica, silica-alumina, titania, zirconia, yttria, lantana, ceria, neodymia, samaria, europia, gadolinia, praseodymia and mixtures thereof. The method described.   24. The method of claim 22, wherein the matrix material is present in an amount less than 70 weight percent.   4. A process according to claim 1 or 3, further comprising recovering the cracking catalyst from the contacting step and treating the spent catalyst in a regeneration zone to regenerate the catalyst.   4. A process according to claim 1 or 3 wherein the cracking catalyst and particulate additive composition are fluidized upon contact with the hydrocarbon feedstock. Further comprising Naru The method of claim 1 or 3 to be contacted with the hydrocarbon feed at least one further NO _x reduction composition. The method of claim 8, wherein the NO _x reduction composition has an average particle size of about 50 to about 200 μm. NO _x reduction compositions has a mean particle size of about 55 to about 150 [mu] m, method according to claim 27. The method of claim 8, wherein the particulate NO _x reducing composition has a Davison Wear Index (DI) value of less than 50. Particulate NO _x reduction composition has a Davison wear index (DI) value of less than 20, The method of claim 29. Particulate NO _x reduction composition has a Davison wear index (DI) value of less than 15, The method of claim 30. FCC cracking catalyst comprises a Y- type zeolite, and NO _x reducing zeolite amount of the NO _x reduction composition is for less than 2 Y- type zeolite in the catalyst particles of the total catalyst in the catalyst particles of the catalyst The method of claim 7, wherein the amount is sufficient to provide a ratio of components. The ratio of the NO _x reducing zeolite component to Y- type zeolite in the catalyst particles of the total catalyst is less than 1, The method of claim 32.   Stage without substantial change in hydrocarbon feedstock conversion or catalytic cracking hydrocarbon yield compared to hydrocarbon feedstock conversion or catalytic cracking hydrocarbon yield obtained from cracking catalyst alone ( 34. The method of claim 33, wherein b) is performed. The method of claim 1, wherein the NO _x reduction composition is incorporated into the FCC cracking catalyst as a component of the cracking catalyst. The amount of the NO _x reduction composition present in the FCC cracking catalyst is at least 0.1 weight percent of the cracking catalyst, the method of claim 35. The amount of the NO _x reduction composition present in the FCC cracking catalyst ranges from about 0.1 to about 70 wt.% Of cracking catalyst A method according to claim 36. The amount of the NO _x reduction composition present in the FCC cracking catalyst ranges from about 1 to about 50 wt.% Of cracking catalyst A method according to claim 37. Furthermore comprising The method of claim 35 that is contacted with the hydrocarbon feed at least one further NO _x reduction composition. NO _x reducing zeolite is stabilized by zinc metal or zinc ions, the method according to claim 7 or 35. The method according to claim 6, wherein the NO _x reduction zeolite is stabilized by zinc metal or zinc ions.